H.K. Beyer, H.G. Karge, I. Kiricsi and J.B. Nagy (Eds.

Catalysis by Microporous Materials

582

Studies in Surface Science and Catalysis, Vol. 94

9 1995 Elsevier Science B.V. All rights reserved.

Adsorption and reaction of thiophene over nickel- and cobalt- containing

zeolites
T. I. Kor&nyia'b, A. Jentysa and H. Vinek~
alnstitut fL~r Physikalische Chemie, Technische Universit&t Wien,
Getreidemarkt 9, A-1060 Wien, Austria
blnstitute of Isotopes of the Hungarian Academy of Sciences,
P.O. Box 77, H-1525 Budapest, Hungary
Ni(Co)HZSM5, Ni(Co)HMOR and NiNaY zeolites were characterized by
thiophene adsorption and hydrodesulfurization (HDS) reaction. The adsorption process
was studied by microgravimetry and infrared (IR) spectroscopy. Thiophene interacts
with H or Na but not with (NiOH) in the unsulfided samples. Ring opening and
oligomerization reactions of thiophene are observed over the acidic ZSM5 and MOR
zeolites. These reactions produce coke during the temperature programmed
desorption (TPD) of thiophene. The HDS with C-S bond cleavage is facilitated by
hydrogenation of thiophene over SH groups in the sulfided NiNaY zeolites.

1. INTRODUCTION

Zeolites containing transition metal offer interesting possibilities to combine acid

properties and a hydrogenation function in bifunctional catalysts. For hydrotreating,
e.g. for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reactions, both
functions are essential: the acid properties are provided by the zeolite, the
hydrogenation activity by the sulfided transition metal cations [1,2]. It can be expected
that these catalysts will be attractive alternatives to alumina supported Co-Mo and NiMo hydrotreating catalysts because of their superior catalytic properties.
During the adsorption and desorption of thiophene on HZSM5 zeolites,
reversible surface reactions of thiophene to unsaturated thiol-like species were found
even at room temperature. Condensation reactions of thiophene to benzothiophene
were observed over HZSM5 only but not over the NaZSM5 samples [3]. Cleavage of
the C-S bond and formation of SH surface groups were observed during thiophene
adsorption on HY zeolites [4].
In this paper we describe the surface chemistry of adsorption of thiophene on
acidic (HZSM5, H-Mordenite (HMOR)) and non-acidic (NAY) zeolites, as well as on
their partially nickel or cobalt exchanged forms. The thiophene HDS activity of Ni or
Co exchanged zeolites was studied and connection was established between the
adsorption and the catalytic properties.

583

2. EXPERIMENTAL
2.1. Materials
HZSM5 (Si/AI = 27.5), HMOR (Si/AI = 10) and NaY (Si/AI = 2.65) zeolites were
partially ion-exchanged with NiCI2 or CoCI 2 solutions. The composition of the ionexchanged zeolites (Table 1) was determined by Scanning Electron Microscopy Energy Dispersive X-Ray Absorption Spectroscopy (SEM-EDS).

Table 1
Composition of the ion-exchanged zeolite samples.
NiZSM5 CoZSM5 NiMOR CoMOR

Ni4Y

Ni8Y

Degree of exchange" (%)

16

20

17

36

31

61

Metal loading (wt%)

0.26

0.33

0.73

1.5

3.7

7.6

"assuming 2 : 1 Ni(Co) : H(Na) stoichiometry

2.2. Characterization
The samples, prepared as self-supporting wafers, were activated in vacuum
for 1 h at 873 K (MOR and ZSM5) or for 4 h at 773 K (Y zeolites). The adsorption of
thiophene at 1 mbar partial pressure and room temperature were investigated by
microgravimetry and IR spectroscopy. After evacuation of the zeolites at room
temperature, the temperature programmed desorption (TPD) of thiophene was carried
out and followed by IR spectroscopy and mass spectrometry.
2.3. Catalytic activity
The catalysts (50 mg) were heated up to 673 K in He at a rate of 6 K/min and
pretreated at this temperature in situ either in He or in a mixture of 5% H2S in H2 for
1 h. Thiophene HDS test reactions were carried out at 673 K and atmospheric
pressure in a flow reactor system (30 cm 3 min -1 flow of 3% thiophene in H2).
Thiophene and the products were detected by GC. The conversion is the fraction of
thiophene converted to coke and gaseous products, the yield is the fraction of
thiophene converted to gaseous products. The catalytic properties were characterized
by activities in C-S hydrogenolysis without C-C bond breaking (yield - (C1+C2+C3
products)), cracking (yield - C4 products), and coking (conversion - yield). The catalytic
conversions determined after 5 minutes time on stream are discussed here, because
all samples deactivated fast due to coke formation.
3. RESULTS AND DISCUSSION

The activated samples (Figure 1) showed IR bands at 3745 cm -1 assigned to

SiOH stretching vibrations and on the acidic samples (ZSM5 and MOR) bands at
3610 cm -1 were assigned to strong BrSnsted acid sites (SiOHAI stretching). On the
ZSM5 and MOR samples the intensities of the SiOHAI bands were decreasing after
ion-exchange, indicating that protons were partially exchanged to metal ions. In the
spectrum of NaY only the band of the SiOH group was present. After ion-exchange

584
u~

4ou

20 a. u.

i.r)

N iSY

,
~.

()

NiMOR

L:
rD

%,

Ni4',~

"

~,

~C.oZSM5

0
@

~ ~
<.1:

CoMOR
NaY

__

---------~-~._.

.~,'oo

36oo

s,oo

s2oo ss'oo

sdoo

s4'oo

Wovenumbers

32'oo M;O-...... ~ g i ~ o - ; ; o 0

.... s~.'oo

(cm-1)

Figure 1. The OH-region of the infrared spectra of activated MOR, ZSM5 and Y
zeolites.
two new bands appeared at 3645 c m -1 and at 3750-3500 c m -1. The first one was
assigned to (NiOH) species [5,6]. The majority of nickel is present in a not well
defined, probably hydrated Ni2+form [5], resulting the broad band at 3750-3500 crn -~.
At 1 mbar thiophene pressure at room temperature the amount of adsorbed
thiophene decreased with increasing metal (Ni or Co) loading of the zeolites (Figure
2). Differences in adsorption capacity may reflect differences in zeolite crystallinity,
empty pore volume and density of adsorbate thiophene. Differences in crystallinity
were not found by XRD. The pore volume of supercages of oxidic Ni(X)NaY zeolites
are identical according to xenon adsorption measurements [7]. The low adsorption
20

aa

,,C

Ni4

15

.2~
O
O

E-~

~o

Ni

~E

Co

O
~,

e~_

Ni

Co

<

MOR

ZSM5

Figure 2. Surface coverage of thiophene at 1 mbar equilibrium pressure.

585

capacity of the transition metal containing zeolites can be attributed to the low (if any)
amount of adsorbed thiophene on the (NiOH) or hydrated nickel species. The
presence of bare Ni2 (or Co 2 ions in the zeolites is not probable under the applied
activation procedure, because paramagnetic nickel species were not identified by 129Xe
NMR in the Ni(X)NaY samples [7,8].
During thiophene adsorption on MOR and ZSM5 (Figures 3 and 4) the
intensities of the SiOH (3745 cm -1) and SiOHAI (3610 cm -~) bands decreased. Parallely
one broad band at 3200 cm -~, thiophene hydrogen bonded to the SiOHAI groups, and
sharp bands at 3122 and 3080 cm ~, CH stretching, and at 1410 cm -~, ring stretching
of thiophene, appeared. The small bands at 1440, 2860, and 2950 cm -1 (Figures 3 and
4) can be assigned to deformation and stretching vibrations of CH 2 groups close to
unsaturated carbon atoms in adsorbed species [3,9,10]. The broad band at 2380 cm -~
is attributed to SH groups [4]. The presence of CH 2 groups may be interpreted by
polymer-like aggregate of thiophene molecules in the presence of acid catalysts [10].
Upon adsorption of thiophene on NiNaY zeolites (Figure 4) the most intense
bands were observed at 3108, 3093, and 1396 cm -~ which resemble similar bands in
the spectrum of liquid thiophene [9,11]. The intensity of the (NiOH) band did not
change. In agreement with these results, the infrared spectra of silica supported nickel
in contact with thiophene did not show any effects which could be attributed to
adsorption onto the metal rather than the oxide surface [10].
Characteristic differences can be seen in the bands of thiophene adsorbed on
ZSM5 and Y zeolites (Figure 4). The splitting of the CH stretching band to symmetric
and asymmetric vibrations is smaller in the Y zeolites (3108 and 3093 cm -~) than in
the ZSM5 samples (3122 and 3080 cm-~). The band of the ring stretching of thiophene
observed at 1410 cm -1 in the ZSM5 samples shifts to 1396 cm -~ in the Y zeolites.
These differences are due to the different adsorption site of thiophene in the two kind
of zeolites (acidic and non-acidic), protons in the ZSM5 (and MOR) samples, and Na
ions in the Y zeolites, respectively. Thiophene was not adsorbed on nickel or cobalt
species as differences were not found in the IR spectra of the metal exchanged and
the original zeolites within the same series.
After evacuation at room temperature a fraction of the thiophene remained
adsorbed on the samples. During TPD, desorption of thiophene only was detected
from the Y zeolites, while from ZSM5 and MOR desorption of benzothiophene was
also observed. This indicates that condensation and cyclization reactions occur on the
surface of ZSM5 and MOR. With MOR about half of the adsorbed thiophene was
cracked to coke, hydrogen, water, and H2S. In the IR spectra of the spent mordenites
(Figure 3) bands at 1584 and 1412 cm -1, ascribed to skeletal vibrations of the
thiophene ring [9], indicated the presence of residual thiophene on the surface after
TPD.
The transition metal free zeolites (HMOR, HZSM5, NaY) did not show any C-S
hydrogenolysis activity for thiophene, but exhibited remarkable coking, and, the acidic
zeolites, additionally some cracking activity.
The initial HDS activities as well as the cracking and C-S hydrogenolysis
activities of NiNaY zeolites increased with the nickel loading (Figure 5). Samples
activated in helium showed much lower activities than the sulfided ones. The
contribution of C-S hydrogenolysis activity to the overall activities was much higher in
the sulfided than in the non-sulfided catalysts. Coking increased with metal loading on

586

3745 3610

t "3122

12380

NiMOR

I .... ---J---'--'k,~

CoMOR
(D
(P
G
O
C)

HMOR
1584 1412 HMOR

O
(f)

_C)
-(.

....

..~

spent

0 . 5 obs. unit

i:i~'oo

Soo

2s'oo

Wovenumbers

2o'oo

~'oo

(cm-1)

Figure 3. Difference of infrared spectra obtained with and without adsorbed thiophene
for MOR zeolites at 1 mbar thiophene equilibrium pressure and the difference
spectrum for the spent HMOR sample.
3122 A3080
,.~6~0 J~//,\""

14 10

23a0

NiZSM5
CoZSM5
HZSM5
(.)
c
(?

Ni8Y

(-)
03

. . . . . t,/ ~

.....

~ k
i

3b()O

. . . . . . . . . .

Ni4Y

_ ~ ~

NoY

3000

25'00

20'00

15'00

Wovenumbers ( c m - 1 )
Figure 4. Difference of infrared spectra obtained with and without adsorbed thiophene
for ZSM5 and Y zeolites at 1 mbar thiophene equilibrium pressure.

587

30

25
c

I~ Coking

20

I'

l--I Cracking

"~
L_ 15
>

lO

Hydrogenolysis

~176 N

mmmIIIIrllllrll

, Iillll.

70
60
50
40
30

10

'

Ni loading (wt%)

'

Ni loading (wt%)

Figure 5. Initial thiophene HDS activities on non-sulfided (left) and sulfided (right)
NiNaY zeolites.
the non-sulfided samples, but did not depend on the metal content on the sulfided
catalysts. Compared to Ni(Co)Mo/AI203 Eurocat reference catalysts the activity of the
faujasite samples was lower, but still much higher than that of the Co/AI203 Eurocat
catalyst.
The activities of Co(Ni)MOR and Co(Ni)ZSM5 zeolites (Figure 6) were lower
than those of NiNaY samples. The reaction of thiophene mainly led to the formation
of coke, with some cracking but hardly any hydrogenolysis activity.
Several parameters influence the catalytic activity of transition metal containing
zeolites in thiophene HDS reactions. These are the loading and sulfidation state of the
metal, the dispersion, distribution and location of the metal-sulfide phase, and the
interaction of this phase with the zeolite support itself and with its acid sites.
The adsorption capacity for thiophene decreases with increasing metal content
(Figure 2), because thiophene is adsorbed on the BrSnsted acid sites or on the Na
ions, but not on the unsulfided, oxidic nickel species (Figures 3 and 4). The unsulfided,
dehydrated nickel species are located at the hexagonal prisms and the sodalite cages
of the Y zeolites up to 14 % of exchange [12]. We agree with this assumption,
because our previous results [8] have shown that the Ni species above this exchange
level are located also in the supercages. Acid sites were not observed on the MOR
35
30
25
o
...,, 20
"- 15
= 10
5

20
i~ Coking

15

Q Cracking

10

Hydrogenolysis

"

"'

IIIIIIIIII1'

CoM

NiM

'

E ~

CoZ

"

'

NiZ

'

CoM

'

111111111111

NiM

CoZ

NiZ

Figure 6. Initial thiophene HDS activities on non-sulfided (left) and sulfided (right) MOR
(M) and ZSM5 (Z) zeolites.

588

and ZSM5 only, but also on the oxidic NiNaY zeolites due to the presence of (NiOH)
species (Figure 1).
In order to obtain high catalytic activity high loading and high sulfidization state
of the metal are the most important factors. The sulfidization of NiNaY zeolites under
the applied pretreatment conditions results in quantitative formation of nickel sulfide
(Ni3S2) according to Welters et al. [13]. The sulfidization can also be carried out by the
thiophene HDS reaction mixture itself (H2S is evaluated in the reaction). But this
process (which takes 5 min only) is much less effective due to the parallel coking than
the one-hour sulfiding by the H2/H2S mixture. As the HDS activities of Co(Ni)MOR and
Co(Ni)ZSM5 zeolites do not change due to presulfidation (Figure 6) we can assume
that these samples are not sulfided effectively under the applied reaction conditions.
The sulfidization of NiNaY zeolites generates acidic properties due to the
formation of additional hydroxyl and sulfhydryl groups [14]. This process also initiates
the migration of nickel species situated in the hexagonal prisms and in the sodalite
cages to the supercages and to the external surface of the zeolite [15]. The C-S
hydrogenolysis activity increases with the metal loading (Figure 5) and is connected
with the sulfided Co or Ni species. Thiophene is adsorbed on the anion vacancies of
sulfided metallic species created by the hydrogen present in the reaction mixture [16].
In the neighbourhood of sulfided species the weak acid sites (SH groups) contribute
to the C-S hydrogenolysis activities.
On the unsulfided MOR and ZSM5 zeolites CH 2 and SH groups are present
(Figures 3 and 4) when thiophene is bound to the strong BrSnsted acid sites. Cracking
and coking are carried out already at room temperature. The SH groups disappear
during TPD (HMOR spent sample in Figure 3)in the form of H2S, which was initially
hydrogen bonded to the SiOHAI groups [17]. In the presence of strong BrSnsted acid
sites and not effectively sulfided Co or Ni species high overall activities cannot be
reached on the Co(Ni)MOR and Co(Ni)ZSM5 zeolites (Figure 6). The strong BrSnsted
acid sites lead to high coking within the overall activities as shown in Figure 6, but
they do not contribute to the C-S bond hydrogenolysis activity. The cracking activities
seem to be connected with both, the strong acidic and weakly acidic sulfided sites, as
they contribute more to the overall activities than the C-S bond hydrogenolysis in the
MOR and ZSM5 samples (Figure 6), but they also increase with the metal loading in
the Y zeolites (Figure 5).
It can be assumed that the role of sulfided species is to facilitate the
hydrogenation of adsorbed thiophene molecule by the weakly acidic SH groups
through the destabilization of the aromatic ring [16]. The following C-S bond
hydrogenolysis occurs easier on the partially hydrogenated nonaromatic species than
on the aromatic thiophene molecule, which is strongly adsorbed on the BrSnsted acid
sites.
4. CONCLUSIONS

(NiOH) species were identified in the IR spectra of activated NiNaY zeolites.

On the (Ni)NaY samples thiophene interacts exclusively with the Na cations but not
with the SiOH or (NiOH) groups. On MOR and ZSM5 zeolites thiophene is hydrogen
bonded to the strong BrSnsted acid sites (SiOHAI groups) but not adsorbed on the
unsulfided Co or Ni species.

589

Surface reactions of adsorbed thiophene occur at room temperature over highly

acidic zeolites only. The most important primary reactions are polymerization and ring
opening. These reactions as well as the adsorption of thiophene are irreversible and
produce coke and weakly adsorbed H2S (SH groups) on the surface of the acidic
zeolites.
The presence of strong Br(Snsted acid sites (SiOHAI groups) leads to coking
and cracking of the molecule of adsorbed thiophene in the zeolites. Thiophene is also
adsorbed on the coordinatively unsaturated sites of the metal sulfide in the
neighbourhood of SH groups. The weak acid sites (SH groups), which are formed
during sulfidization, at least partially hydrogenate the molecule of thiophene adsorbed
on the anion vacancies of the metal sulfide. Therefore for the hydrogenolysis of the
C-S bond of partially saturated thiophene, sulfided Ni (Co) species are indispensable.
ACKNOWLEDGEMENTS

The authors are indebted to Dr. V.H.J. de Beer for generously providing the Ni(X)NaY
samples. This work was supported by the "Fonds zur F(Srderung der
Wissenschaftlichen Forschung" under project FWF P9167. T.I.K. thanks the Lise
Meitner postdoctoral fellowship (M00091-CHE) for the Austrian Science Foundation.
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